Complex zinc- and silver-ammonia salts of alkenyl succinic acids, methods for preparing them, and method for combating fungi therewith



Patented Oct. 13, 1953 UNITED STATES PATENT OFFICE COMPLEX ZINC- ANDSILVER-AMMONIA SALTS F ALKENYL SUCCINIC ACIDS, METHODS FOR PREPARINGTHEM, AND METHOD FOR COMBATING FUNGI THEREWITH Mearl A. Rise,Portsmouth, Va., assignor to Allied Chemical & Dye Corporation, NewYork, N. Y., a corporation of New York N 0 Drawing. Application December1, 1949, Serial No. 130,602

15 Claims. (01. 167-22) plant-mfesting fungi by the application ofsulfur- The complex ammonia salts illustrated above containing,copper-containing and other chemimay be prepared by any suitab processFor l i i example, they may readily be prepared by mm- In my copendingapplication Serial No. 130,601 ing the corresponding alkenyl succinicacid in an filed as of even date herewith, there are described, aqueoussolution with ammonium hydroxide and as new compositions of matterhaving fungicidal a water-soluble silver or zinc salt, or they mayproperties, the dibasic silver salts of alkenyl suc 8 prepared byreactmg ammonium hydroxide inclusive in the alkenyl group and a methodfor sponding alkenyl succinic acid in aqueous solut the t The dibasicsilver salts of the alkenyl succinic The dibasic silver salts of alkenylsuccinic acids f ds m y be prepar d ac d ng to my p ldof my copendingapplication referred to above, pp fi above referred y rea n however, areonly slightly soluble in water d between the corresponding alkenylsuccinic acid ient because of the tende'ncy of t relatively dium saltwith a water-soluble silver salt such as insoluble salts to settle outof suspension. Morel e nitrate d the dibaSic Z1116 Salts y be over, whenapplied in this manner, the silver salts Similarly p p do not adherestrongly t t m m, and may be The alkenyl succinic acid anhydrides arereadremoved byrain or Watersprays ily prepared according to the methoddescribed I have now found that the ad antageously toxic m Patent 2 411215 Of Meg 159 d with no separation of fungicide and liquid, wheregoingthrough the dibesic sodium d n salts insolub e, rain resistant dzbasicsalt on the foliage. alkanl/l 5110011119 301d l fimlnonlum The use ofthese ammonia comple es therefore of- FOXlde and & Water-soluble Z1110Salt Sufih as fers the twofold advantage of permlttlng applica Z1110Sulfate: he silvemmmoma salt 1s most tion from aaueous solutions,forexample bysprays, 40 {Emily prepared from the Corresponding dibasic Iand of alfordin an adherent coat n which resists Silver saltremova byram to a considerably greate extent In carrying out the preparation ofthe complex ban when annhed m suspens on fo m More silver ammonia saltsof alkenyl succinic acids,

the djbagj Zinc salts f the alkenyl succinic acids 4 .115 salt, thedesired dibasic silver salt of alkenyl ammonia complexes place by simplymixing the reactants at ordinary The complex sil and Zinmammoma Salts 5room temperature (about 25 (3.), whereupon the of alkenyl succinic acidsof my invention have solutlon may be filtered and may be diluted Withthe structural formula set forth below: water to the particularconcentration at which it E O r is to be used as a fungicide.

I H The zinc-ammonia complex salt is preferably R o 00\ prepared byadding to alkenyl succinic acid an- My (NBS), hydride a quantity ofwater sufficient to hydrate at least about 25% of the cnhydride andheating to effect such hydration; the resulting alkenyl succinic acid orpreferably a mixture of alkenyl centration' for storage or us (3 {issuccinic acidand allienyl succinic acid anhydride: is cooled to roomtemperature (about 25 C.) an ammoniacal zinc solution is prepared byaddingii to aqueous ammonium hydroxideefior. example containing about20-30% sine salt such as zinc suliateeand';stirringjhee mixture untilsolution takes =1p1LC8;.llO ithis'zam=- moniacal zinc salt solution, thealkenyl succinic acid-alkenyl succinic acid anhydride mixture. (1%!"scribed above is a over a period of about two hours while the tem--perature is held at or below normahroomtemperature (about 25 C.). Themixture is stirred until a clear solution results, containing thecomplex zinc-ammonia salt of alkenyl This solution may be diluted to thedesired con- The mete l-ammonia complex salts of allienyl su'ecinlc:acids of l the type contemplated. herein" are new compositionsatnormalroom temperature (about 25 Cf) and they are all water-soluble toan extent: g-r eatly iri excess'oftlie concentrations required to efiectadequatecontrol oi various fungus organisms. The when exposed tc theatmosphere and this characte'ristic contributes to: their usefulness indi positing tightly adhering films of thetoxic di--- basic metalSEt'1t'S-Ol l-"-tl1laV8s and otlier'spart's oi plants and tl le like; tobe protectedgfrom :funa 30 gusi-growtlisi However, in aqueous solutions;the metal-ammonia complexes are amply stable for ccrn'unercis1*:storage" and sl'iipmena e en at concentrations" gr that at whichthey: ar'ei to"v be i used':

While Fany' single?m'etal amrnonia complex salt of: the. character:described may be used as aruirgicidei 'according t'o my invention;mixtures are contemplatedlandkvill gener'ally be used; pr r--' ticularlythose prepared fromolefins derived from cracked distillates containingmixtures of1n1on0- olefins: In.- such: instances; it is convenient tousesfractions': or cuts containing' th'e desired" prerdominant number ofcarbon atoms in the chains;

cuts: containing predominantly carbonetornsr being" preferred; and".anyof "the cuts, or mixtures of theiwhole rang'e or parts thereof; ofcompound containing. from 4: to 24 carbcnlatomsc inclusive-are;satisfactory:

The following-- specific examples will illustrate 60 the preparationziofthe complex? ammonia:- salts Ear-ts are given: by? weight;

EXAMPLE- 1 90-parts of the dibasic silver" salt: off a Ce-s alkeny1-succinic-acid (MA-3%. Ag) was? dissolved in 450 parts or" an ammoniumhydroxide solution (sp. gr. 0.90) whereupon the silver-ammonia complexof: alken'yl succini'c' acidwas formed.

The solution was filtered and diluted with water 5 Table l.LD.-95- (in;terms:

Materisl'tested AETNHS complex of Cm ASN-"( 'rodl oi' *Alkenylsuccinicfacid;

dded gradually;with stirring;

succinic acid.

which are sol-1ds rrnmoniacomplexes as I such are: unstabletci.151times-iitsweight; The resultinasolfition was relatively stable atthis concentration and even more stable when further diluted.

EXAMP. LE 2 droxide solution. and 1 stirring until solutionawase.

completed. To thisa-selution the allienyi succinic,acid-alkenyl-succinic acid anhydridasolutiondew scrl'b edab'ove wasadded gradually; with stirring over: aperiod-oi two hours .while. thetemperature washeldwatorzbelow room temperature.(25? (1.); The:mixture.- was. stirred at room. temperature. until a clear formation:of; the;zinc+ammonia. complex. of! the predominantly Clo-'12allienyl.succinicacidi.

The: new silverand: zineearnmoniaecomplexes.. of: alkenylsuccinic acids.are -effectiveafungicides. 2 gains-t a nurnberlofiungus organismsheretoiore.

difiicultto control. This activity issobtainedby, application ofsolutions. containing. low. concene trations and danger to the plant isnotlalhazard. evenwithathe silver salt at .concentrati'ondevel's 3suiflcientstoinsure complete: control=oithe.organ-.

ism. This-effective fungicidal protectionist-ai iordedagainstearly-blight of .tomatoes .by. applie cation sat concentrations of.about 0 .05.%si1ver;

against .snapdragon .rust at concentrations of bee and about .i 0.011%.silver; a

tween. .about 0.0055517, andsagainst .lateblight.ottomatoes-et.concentra:

tions. of about;0l002&%; silver. in the-solution-and at slightly higherconcentrationsot'zincqas-indie.

cated-iinTable.Lbelow. The. new compositions. of

my inventioniareiparticularlyvaluable for. useas,

watenspraysess theseitwol salts are;water.sclub1e.-

andcan besprayed onlplantswithno. sep aration. oi afungicideeand liuidodiluent, whereupon ithei water... andammonia. evaporate leaving ,therelatively insoluble tightly adherentrainresistantdie be sic salt. onthe. foliage.

The .iolloivingiungicidal(tests .were carried cut-.- using a. watersolution. of ,the silvereammonia.

complexof.aiceisialkenyl .succinic acid and. a so-- lutionsof atzlnc-ammoniaa-complex of air-C1042. allienylisuccinic aoid.-. In Table-1 below are listed: the amounts.' ofthe particular fungicidal prep-aration-in. spray solution: appliedito: theplant foliagerequired;torpi'event .95 %z or spore: germi nation: (113 951) offth'ethree-fungus organisms:

01 fungicidal preparatiomn spra ned 'perccntmetalizn orAg);

Organism used..-

Snapdragcnrust Tomato early blight: 'Tomatodateblightr f f 35233 Percent333 Percent 8:3 Percent aration metal aration metal aration metalsolution resulted indicating the,

The relative rain ons made with complexes which were obtained asfollows.

leaves from the Primula obconz'ca were areas were each leaf was withwater equivalent to one rainfall.

to compare the water resistance. The data obtained are tabulated inTable II below:

Table II. Leaching of Zn salt of Clo-12 allcenyl succinic acid fromplants and wherein R represents an alkenyl group having from 4 to 24carbon atoms inclusive, and a: repnot greater than 6. The composition ofclaim 1 wherein the metal is zinc.

3. The composition of claim 1 wherein the metal is silver.

4. As a new composition of matter, a mixture of complex silver-ammoniasalts of alkenyl succinic salts having the following formula wherein R,represents a containing atoms and than 6.

plurality of alkenyl groups predominantly from 10 to 12 carbon 2:represents an integer not greater wherein R from 4 to 24 groupconsisting the following general formulas (NEH)- R rep taining prresents a plurality of edominantly from alkenyl groups 6 to 8 COD--carbon atoms.

10. In a process for'preparmg complex metalalkenyl" succinic aacidsselected ammonia salts of from the group the following ge .alkenyl succiadding to cal solution of no i H consisting of silve ammonium of one ofsai ture until the reac 11. The method R represe taining predom zin 12.

atoms.

which pound s pounds havin comprises and wherein R represents from 4 to24 carbonatoms inclusive, and a:

resents an i 24 carbon nteger not greater than (a) mixing thecorresponding hydroxide with d metals, and (d) agitating tion iscomplete.

wherein the metal atoms inclusive, and m partial hydration consisting:of compounds having neral formulas wherein: 'Rrrepresents an :alkenyl.group having fromi to resents an i which comprise nic acid anhydridewith. water,

effect whereby a-mixture of allienyl succinic acidacid anhydride isformed,

formed an ammoniarep- 6, the steps thereof metal selected from the groupr and zinc prepared a water-soluble of claim 10 by mixing salt the mix-The method according to claim 10 wherein nts aplurality oi alkenylinantly from con- 10 to 12 carbon 13. A process for combating fungi onplants,

applying to theplanta comgeneral formulas (NHZ):

14. A process 1 nteger not greater than 6.

or combating fungi on pl elected from the group consisting of comg the.

an alkenyl group having repants,

adhering rain resistantcoatmg oi the-correspond which :comprisesspraying the plant with 'an aqueous 1 solution containing-a I compoundselected from the group consisting 'of compounds having the. generalformulas g a 'n io-o Ag rac d- A8 o and wherein R represents analk'enyl: group having from 4 to 2 icarbon' atoms inclusive,and'mrepresents an integer not greatepthanfi, exposing the plants to'theatmospherewhereby the complex ammonia salt decomposes; leavingatightlytomato plants which comprises :appl

anaqueous soa dibasic metal the group consisting of silver acidcontaining 24 carbon atoms, inclusive, in the alk'enyl-group, whereinthe molecular ratio of ammonia to alk'enylsuccinic acid salt in thecomplex is at least one and not more than '6.

MEARL AHKISE.

References Cited in the file of this patent OTHER "REFE-YtIEIPICE SBeilstein: 2 Band, 4 Auflage, page 607. Ber., vol. 5, January-June 1872,pages 30-31.

American Chcm. 'Journ., vol. 39, J anuary-June 1908, pages 201- 203.

Dimond et al.: Rept'Eun'gicide Sub-committee Am. Phytopathological Soc;Conn. Agr. Expt. Sta, Mimeo Puh, June 22, 1942, pp. 1, 2, and 4.

Frear, Chemistry of Insecticides, Fungicides, and Herbicides, 2ndedition, 1948, D. Van Nostrand, N. Y., p. 255.

1. AS NEW COMPOSITIONS OF MATTER, THE COMPLEX METAL-AMMONIA SALTS OFALKENYL SUCCINIC ACIDS SELECTED FROM THE GROUP CONSISTING OF COMPOUNDSHAVING THE FOLLOWING GENERAL FORMULAS